CN109960137B - Method for manufacturing balance wheel of clock - Google Patents
Method for manufacturing balance wheel of clock Download PDFInfo
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- CN109960137B CN109960137B CN201811455309.4A CN201811455309A CN109960137B CN 109960137 B CN109960137 B CN 109960137B CN 201811455309 A CN201811455309 A CN 201811455309A CN 109960137 B CN109960137 B CN 109960137B
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 88
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- 230000009477 glass transition Effects 0.000 claims abstract description 18
- 230000008025 crystallization Effects 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- 229910052726 zirconium Inorganic materials 0.000 claims description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 12
- 229910045601 alloy Inorganic materials 0.000 description 16
- 239000000956 alloy Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000010453 quartz Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000005300 metallic glass Substances 0.000 description 4
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000003856 thermoforming Methods 0.000 description 3
- 238000000708 deep reactive-ion etching Methods 0.000 description 2
- 230000005489 elastic deformation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 241000270728 Alligator Species 0.000 description 1
- 229910000942 Elinvar Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B17/00—Mechanisms for stabilising frequency
- G04B17/04—Oscillators acting by spring tension
- G04B17/06—Oscillators with hairsprings, e.g. balance
- G04B17/066—Manufacture of the spiral spring
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B17/00—Mechanisms for stabilising frequency
- G04B17/04—Oscillators acting by spring tension
- G04B17/06—Oscillators with hairsprings, e.g. balance
- G04B17/063—Balance construction
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B17/00—Mechanisms for stabilising frequency
- G04B17/20—Compensation of mechanisms for stabilising frequency
- G04B17/22—Compensation of mechanisms for stabilising frequency for the effect of variations of temperature
- G04B17/222—Compensation of mechanisms for stabilising frequency for the effect of variations of temperature with balances
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B17/00—Mechanisms for stabilising frequency
- G04B17/20—Compensation of mechanisms for stabilising frequency
- G04B17/22—Compensation of mechanisms for stabilising frequency for the effect of variations of temperature
- G04B17/227—Compensation of mechanisms for stabilising frequency for the effect of variations of temperature composition and manufacture of the material used
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B18/00—Mechanisms for setting frequency
- G04B18/006—Mechanisms for setting frequency by adjusting the devices fixed on the balance
-
- G—PHYSICS
- G04—HOROLOGY
- G04D—APPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
- G04D3/00—Watchmakers' or watch-repairers' machines or tools for working materials
- G04D3/0002—Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe
- G04D3/0035—Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of the regulating mechanism
- G04D3/0038—Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of the regulating mechanism for balances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D15/00—Casting using a mould or core of which a part significant to the process is of high thermal conductivity, e.g. chill casting; Moulds or accessories specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D25/00—Special casting characterised by the nature of the product
- B22D25/02—Special casting characterised by the nature of the product by its peculiarity of shape; of works of art
- B22D25/026—Casting jewelry articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
-
- G—PHYSICS
- G04—HOROLOGY
- G04C—ELECTROMECHANICAL CLOCKS OR WATCHES
- G04C3/00—Electromechanical clocks or watches independent of other time-pieces and in which the movement is maintained by electric means
- G04C3/04—Electromechanical clocks or watches independent of other time-pieces and in which the movement is maintained by electric means wherein movement is regulated by a balance
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Adornments (AREA)
- Forging (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Micromachines (AREA)
Abstract
The invention relates to a method for manufacturing a metal alloy balance wheel by moulding, comprising the following steps: a) a mould made in the negative shape of the balance (1); b) obtaining a metal alloy having a coefficient of thermal expansion of less than 25ppm/° c and capable of being in an at least partially amorphous state when heated to a temperature between its glass transition temperature and its crystallization temperature; c) placing said metal alloy in said mould, heating said metal alloy to a temperature between its glass transition temperature and its crystallization temperature, so as to be thermally moulded and form a balance; d) cooling said metal alloy to obtain a balance (1) made of said metal alloy; e) releasing the balance (1) obtained in step d) from its mould.
Description
Technical Field
The invention concerns a method for making a balance for a timepiece, the balance comprising a felloe, a hub and at least one arm connecting the hub to the felloe.
Background
The oscillator or resonator of a mechanical timepiece consists of a spiral spring and a flywheel called a balance. Temperature changes change the stiffness of the spiral spring and the geometry of the balance spring and balance wheel, which changes the spring constant and inertia, and thus the oscillation frequency. Clock manufacturers strive to obtain temperature stable oscillators, and have explored/utilized several approaches, one of which obtains the Nobel prize, developed for the Charles-Edouard Guillame Elinvar alloy, which has an elastic modulus that increases with temperature and compensates for the increase in balance inertia. The development of oxidized, and therefore thermally compensated, silicon has since exceeded the performance of the alligator alloy and has the advantage of being less sensitive to magnetic fields. The spiral spring made of monocrystalline quartz also allows thermal compensation of the inertial variations of the balance. But in contrast to oxidized silicon, which has an oxidation thickness that can vary depending on the material of the balance used, quartz spiral springs are limited to materials with a coefficient of thermal expansion of about 10 ppm/deg.c, for example corresponding to titanium and platinum. The main problems with these materials are processability and control of fine structure and/or finishing processes (e.g. mirror polishing). In the case of titanium, its relatively low density limits its use for large balances, and in the case of platinum, its high price limits its use to prestige and luxury goods.
Disclosure of Invention
The aim of the present invention is to remedy these drawbacks by proposing a method for making a balance wheel using new materials, allowing simpler and more precise manufacturing, for example to reduce the variations in momentum and/or variability in the same production batch.
To this end, the invention firstly relates to a method for manufacturing a balance for a timepiece, the balance comprising a rim, a hub and at least one arm connecting the hub to the aforementioned rim, the rim, hub and arm being made of a metal alloy, the method comprising the following steps:
a) a mould made in the negative shape of the balance wheel (negative shape);
b) obtaining a metal alloy having a coefficient of thermal expansion of less than 25ppm/° c and capable of being in an at least partially amorphous state when heated to a temperature between its glass transition temperature and its crystallization temperature;
c) placing a metal alloy in a mould, heating said metal alloy to a temperature between its glass transition temperature and its crystallization temperature, so as to be thermally moulded and form a balance;
d) cooling said metal alloy to obtain a balance made of said metal alloy;
e) releasing the balance obtained in step d) from its mould.
The invention also relates to a method for manufacturing a balance for a timepiece, the balance comprising a rim, a hub and at least one arm connecting the hub to the aforementioned rim, the hub and the arm being made of a metal alloy, the rim being made of a material having a density higher than the density of the aforementioned metal alloy of which the hub and the arm are made, said method comprising the following steps:
a) a mold made in the negative shape of the balance;
a') inserting a rim or rim portions made of a material having a density higher than that of the above-mentioned metal alloy into the mould;
b) obtaining a metal alloy having a coefficient of thermal expansion of less than 25ppm/° c and capable of existing in an at least partially amorphous state when heated to a temperature between its glass transition temperature and its crystallization temperature;
c) placing a metal alloy in a mould, heating said metal alloy to a temperature between its glass transition temperature and its crystallization temperature so as to be hot-moulded, and overmoulding said felloe or felloe portion so as to mould a balance with an insert;
d) cooling the metal alloy to obtain a balance wheel with an insert;
e) releasing the balance obtained in step d) from its mould.
Due to the nature of amorphous metals, metal alloy balances can be produced using simplified manufacturing methods (e.g., casting methods or hot molding methods). Furthermore, one characteristic of a metal alloy in its at least partially amorphous form is that it has a significantly wider range of elastic deformation than its crystalline equivalent, due to the absence of dislocations. This characteristic makes it possible to perform overmoulding or integration so that it is possible to improve the centring and to control the inertia and/or unbalance elements in the balance.
Drawings
Other features and advantages will become apparent from the ensuing description, given for indicative and non-limiting purposes only, with reference to the accompanying drawings, in which:
fig. 1 is a perspective view of a balance made according to the invention;
fig. 2 is a partial top view of an alternative balance made according to the invention;
fig. 3 is a partial top view of another alternative balance made according to the invention;
FIG. 4 is a section along the axis A-A in FIG. 3; and
figures 5 to 10 are partial top views of other balance wheel alternatives made according to the invention.
Detailed Description
Fig. 1 shows a balance 1 for a timepiece. Such balance 1 conventionally comprises a continuous or discontinuous felloe 2 defining the outer diameter of balance 1 and a hub 4 constituting a central part thereof and containing a hole 6 defining the pivot point of balance 1, which receives a shaft (not shown). The hubs 4 are commonly connected to the rim 2 by arms 8. In this example, there are four arms 8 at 90 ° to each other. There are also balances with two or three arms, arranged at 180 ° or 120 °, respectively.
According to the first embodiment, the rim 2, the hub 4 and the arms 8 are made of the same metal alloy. Balance 1 is advantageously a one-piece component, i.e. it is manufactured in one piece.
To this end, according to a first embodiment of the invention, the method of manufacturing balance 1 in which rim 2, hub 4 and arm 8 are made of the same metal alloy comprises the following steps:
a) a mould made in the negative shape of balance 1, said mould comprising a possible decorative surface structure;
b) obtaining a metal alloy having a coefficient of thermal expansion typically below 25ppm/° c and capable of being in an at least partially amorphous state when heated to a temperature between its glass transition temperature and its crystallization temperature;
c) placing a metal alloy in a mould, heating said metal alloy to a temperature between its glass transition temperature and its crystallization temperature, so as to be thermally moulded and form a balance;
d) cooling said metal alloy to obtain a balance 1 made of said metal alloy;
e) releasing balance 1 obtained in step d) from its mould.
The cooling step d) may be carried out at a cooling rate selected to obtain a crystalline, partially amorphous or fully amorphous alloy.
For example, balance 1 may also be made entirely of an alloy containing titanium or zirconium, as will be described in detail below. Since zirconium, for example, has a relatively low density, the zirconium alloy used in the present invention also has a relatively low density (6.5 g/m)3) It is therefore proposed to add components made of a more dense material to increase the inertia of the balance, in particular if it is desired to have a small size for a small movement. These components make it possible to increase the inertia of the balance while maintaining an aesthetic rim geometry and good aerodynamic characteristics.
Thus, according to a first alternative shown in fig. 2, the rim 2 can comprise an overmoulded first inertia adjusting member 10, the first inertia adjusting member 10 being made of a material having a density higher than that of the metal alloy. These first inertia adjusting members 10 may be made of tungsten or tungsten carbide, for example, and obtained by over-molding.
To achieve this object, the method of the present invention comprises: a step of overmoulding the above-mentioned first inertia adjustment member 10 into the rim 2 by means of an insert placed in the mould before the metal alloy is introduced and overmoulded, said first inertia adjustment member 10 being made of a first material having a density higher than that of the above-mentioned metal alloy.
According to a second embodiment, the arms and the hub of the balance are made of a metal alloy and the rim is made of a material having a density higher than the density of the metal alloy used for the arms and the hub. The material itself may be a metal alloy containing platinum or palladium or other material as defined below. The arm and the hub of the balance are made, for example, of an amorphous metal alloy containing zirconium, as defined below, so as to allow the balance to be paired with a spiral balance spring, preferably made of monocrystalline quartz, and, in order to improve the inertia of the balance, the rim is made of another material having a density greater than that of the zirconium-containing metal alloy used for the arm and the hub.
In order to achieve this, according to a second embodiment of the invention, the hub 4 and the arms 8 of a balance for a timepiece are made of a metal alloy, the rim 2 being made of a second material having a density higher than that of the metal alloy from which the hub 4 and the arms 8 are made, the method for manufacturing such a balance comprising the following steps:
a) a mould made in the negative shape of balance 1;
a') inserting a rim or rim portions made of a material having a density higher than that of the above-mentioned metal alloy into a mould;
b) obtaining a metal alloy having a coefficient of thermal expansion of less than 25ppm/° c and capable of being in an at least partially amorphous state when heated to a temperature between its glass transition temperature and its crystallization temperature;
c) placing a metal alloy in a mould, heating said metal alloy to a temperature between its glass transition temperature and its crystallization temperature so as to be hot-moulded, and overmoulding the felloe or said felloe portion so as to mould a balance with an insert;
d) cooling the metal alloy to obtain a balance wheel with an insert;
e) releasing the balance obtained in step d) from its mould.
The cooling step d) may be carried out at a cooling rate selected to obtain a crystalline, partially amorphous or fully amorphous alloy.
The method according to the invention according to the first or second embodiment advantageously exploits the characteristics of a metal alloy which, when heated, can be at least partially in amorphous form, in order to produce a balance made of a metal alloy.
Indeed, metal alloys that are capable of being in an at least partially amorphous form when heated allow for greater ease of molding by allowing parts having complex shapes to be produced with greater precision. This is because of the special property of "amorphous metals" which can be softened while remaining amorphous for a certain period of time in a particular temperature interval [ Tg-Tx ] specific to each alloy (for example, for Zr-containing alloys: Tg 440 ℃, Tx 520 ℃). They can therefore be shaped at relatively low stress and not too high a temperature, allowing simplified processes, such as thermoforming, to be used. Furthermore, the use of such a material makes it possible to reproduce the fine geometry rapidly and precisely according to the temperature within the temperature interval [ Tg-Tx ], the alloy therefore having all the details of the negative shape. For example, for a platinum-containing material as defined below, the molding is carried out at about 300 ℃ with a viscosity of up to 103Pa · s and a viscosity of 1012Pa · s at a pressure of 1MPa, instead of at the temperature Tg. The use of a die has the advantage of producing three-dimensional parts with high precision, which cannot be achieved by cutting or punching.
The method advantageously used is the formation of amorphous preforms. The preform is obtained by melting in a furnace the metallic components constituting the metallic alloy. The melting is carried out under a controlled atmosphere in order to obtain as low as possible an oxygen contamination level of the alloy. Once these components are melted, they are cast into the shape of a semi-finished product and then rapidly cooled to partially or completely maintain the amorphous state. Once the preforming is completed, thermoforming is carried out, with the aim of obtaining the final part. The hot molding is performed by pressing for a period of time in a temperature range between the glass transition temperature Tg and the crystallization temperature Tx of the metal alloy such that an at least partially amorphous structure is maintained. This is done to maintain the elastic properties of the amorphous metal.
In the case of Zr containing alloys and temperatures of 440 c, the pressing time generally need not exceed about 120 seconds. Thus, the thermal molding makes it possible to maintain the initial amorphous state of the preform. The various forming steps of the cast solid balance according to the invention are then:
1) the mould with the negative shape of the balance is heated to a selected temperature,
2) the amorphous metal preform is placed between hot dies,
3) applying a clamping force to the mold to impart the geometry of the mold to the amorphous metal preform,
4) waiting for the maximum time of the pre-selection,
5) the mould is opened and the mould is opened,
6) a cooling balance wheel, and
7) the balance is removed from the mould.
The balance wheel may of course also be produced by casting or injection. The method comprises casting or injecting a heated metal alloy at a temperature between its glass transition temperature and its crystallization temperature such that it can be at least partially amorphous in a mold having the shape of the final part.
The mold may be reused or dissolved to release the part. The moulding method has the advantage of perfectly reproducing the balance geometry, which includes possible decorations or surface structures. A smaller degree of inertia and centering variation is obtained in the production batch of balances. The moulding method makes it possible to obtain a balance with an aesthetic geometry, sharp internal angles, rim profile and/or convex arm profile and perfect final surface. A discontinuous rim may also be provided. To achieve the highest quality, the mold will be made of silicon by the DRIE [ deep reactive ion etching ] method. It is self-understood that the mold may also be constructed by mechanical milling, laser machining, electro-erosion, or any other type of machining.
The elastic properties characteristic of amorphous metal are used for overmoulding or integrating functional and/or decorative elements in the rim and/or at the position of the arms and/or at the position of the hub, for example by placing a suitable insert in the mould before the heated metal alloy is made at least partially amorphous between its glass transition temperature and its crystallization temperature.
Independently of the first or second embodiment of the method of the invention, the rim 2 can comprise a groove 12, the groove 12 being designed to receive a second member 14, 15 for adjusting the inertia and/or the unbalance, as shown in figure 3. These grooves 12 can advantageously be provided during the manufacture of balance 1 by moulding according to the method of the invention. The second means 14, 15 for adjusting inertia and/or unbalance may be, for example, a counterweight, a split counterweight acting as a counterweight, a pin 14, a cotter pin or an unbalance adjustment pin 15. These components are pressed or clamped into the respective recesses 12. Fig. 3 shows the pin 14 inserted into its groove 12, and the unbalance adjustment pin 15 inserted into its groove 12. Fig. 4 shows a cross section along the line a-a of fig. 3. Fig. 3 shows the unbalance adjustment pin 15 inserted in the groove 12 of the rim 2.
It is evident that these means for increasing the inertia of the balance are preferably used in the case where the felloe is made of a material with a low density, such as titanium or zirconium, but they can also be used in the case where the felloe is made of another material.
To increase the inertia of the balance, it is also possible to provide a thicker or wider rim, in particular in the case of a larger balance.
The recess 12 shown in fig. 3 may also be a recess designed to receive an aesthetic and/or light emitting element, such as a tritium tube (not shown) or a capsule of phosphorescent (e.g. high-intensity noctilucent) or fluorescent material.
According to another aspect of the invention, one or another step of the method comprises the step of overmoulding the flexible centring members 16, 17 onto the periphery or surface of the hub 4. Thus, the hub 4 may comprise an integrated flexible centring member which allows the balance to self-centre on the axis during its assembly, due to the elastic deformation of the above-mentioned flexible centring member.
According to fig. 5, the above-mentioned integrated flexible centering members 16 are shown as elastic strips within the inner circumference of the hub 4, such that the integrated flexible centering members 16 are located in the holes 6. According to fig. 6, the above-mentioned integrated flexible centering members 17 are located on the surface of the hub 4 and distributed around the hole 6. According to the method of the invention, flexible centring members 16 and 17 can advantageously be inserted by moulding during the manufacture of balance 1.
According to another aspect of the invention, one or other of these methods comprises a step of overmoulding a third flexible inertia adjustment member 19, 20, 22a, 22b in the arm 8. At least one of the arms 8 thus carries an integrated third flexible inertial adjustment member.
According to fig. 7, the end of the arm 8 on the side of the rim 2 ends in two branches 8a, 8b, between which branches 8a, 8b a space 18 is formed, in which space 18a third "V" -shaped flexible bistable inertial adjustment element 19 is integrated for the purpose of adjusting the frequency.
According to fig. 8, the space 18 accommodates a third flexible inertial adjustment member 20 for the purpose of adjusting the frequency. To this end, the third inertia adjustment member 20 is made of a material such as silicon or silicon oxide having different expansion characteristics than the metal alloy of the balance of the invention.
According to fig. 9, the end of the arm 8 on the side of the rim 2 ends in three branches 8a, 8b, 8c, between which three branches 8a, 8b, 8c two spaces 18a, 18b are formed, in which two spaces 18a, 18b a third flexible multistable inertia-adjusting ratchet member 22a, 22b is integrated for the purpose of adjusting the frequency.
According to the method of the invention, these third flexible inertial adjustment members 19, 20, 22a, 22b for adjusting the frequency can also advantageously be put in place by moulding during the manufacture of balance 1.
These third flexible inertia adjustment members 19, 20, 22a, 22b for adjusting the frequency can be used when the whole balance is made of the same metal alloy and when the arms are made of one metal alloy and the rest of the balance, in particular the rim, is made of another material. .
According to another alternative of the invention, a mold having a microstructure forming a decorative element or photonic grid is used in one or another method of the invention. Thus, one of the arm 8, the rim 2 and the hub 4 has a structured surface quality. Only one part may have a structured surface quality or all parts of the balance may have a structured surface quality, which may be the same or different. Fig. 10 shows a balance of the invention, in which the felloe 2 has a structured surface quality different from that of the arm 8. Such structured surface quality may be in the form of polished, sanded, frosted, beaded, sunglowing, and the like. Microstructures forming a photonic network may also be provided in the mould used to make the balance, in order to replicate these microstructures on the surface of the balance. These microstructures may allow the creation of photonic crystals, giving the component a certain colour, hologram or diffraction pattern, which may constitute a security feature. These structures are introduced directly into the mould and are replicated by thermoforming during the production of the balance, which does not require any additional finishing operations. A logo may also be added to the mold.
The metal alloy used in the process of the invention typically has a coefficient of thermal expansion of less than 25 ppm/c and greater than 7 ppm/c and is capable of existing in an at least partially amorphous state when heated to a temperature between its glass transition temperature and its crystallization temperature.
The metal alloy used in the process of the invention is preferably based on an element selected from the group consisting of platinum, zirconium, titanium, palladium, nickel, aluminum and iron.
In the present description, the expression "based on an element" means that the above-mentioned metal alloy contains at least 50% by weight of the aforementioned element.
The above-described metal alloys for use in the present invention may be platinum-based and may have a coefficient of thermal expansion of less than 12 ppm/deg.C, preferably between 8 ppm/deg.C and 12 ppm/deg.C.
Such platinum-based metal alloys may consist of, in atomic percent:
platinum as the basic component, the amount of which constitutes the balance,
-13% to 17% of copper,
-3% to 7% of nickel,
-20 to 25% phosphorus.
The metal alloys used in the present invention may also be based on zirconium and may have a coefficient of thermal expansion of less than 12 ppm/c, preferably between 8 ppm/c and 11 ppm/c.
Such a zirconium-based metal alloy may consist of, in atomic percent:
zirconium as the basic component, the content of which constitutes the balance,
-from 14% to 20% of copper,
-12% to 13% of nickel,
-9% to 11% of aluminium,
-2% to 4% niobium.
The metal alloys used in the present invention may also be based on palladium and may have a coefficient of thermal expansion of less than 20 ppm/c, preferably between 13 ppm/c and 18 ppm/c.
Such palladium-containing metal alloys may consist of, in atomic percent:
palladium as the basic component, the content of which constitutes the balance,
-25% to 30% of copper,
-from 8% to 12% of nickel,
-18% to 22% phosphorus.
Ideally, the alloys used in the present invention do not contain any impurities. However, they may include trace impurities which are usually inevitably derived from the preparation of the above-mentioned alloys.
The alloys used in the present invention can be used to make at least part of a balance paired with a spiral spring, preferably made of monocrystalline quartz, if they have a coefficient of thermal expansion less than 12 ppm/deg.c and greater than 8 ppm/deg.c. The alloy used in the invention, which has a coefficient of thermal expansion of less than 20 ppm/deg.C and greater than 13 ppm/deg.C, can be used to make at least part of a balance to be paired with a spiral spring made of metal or silicon.
More preferably, the platinum-based metal alloy used in the present invention includes, in atomic percent: 57.5% Pt, 14.7% Cu, 5.3% Ni, and 22.5% P.
The coefficient of thermal expansion of this alloy is between 11 ppm/deg.C and 12 ppm/deg.C.
The above-mentioned zirconium-based metal alloy used in the present invention more preferably includes, in atomic percent: 58.5% Zr, 15.6% Cu, 12.8% Ni, 10.3% Al and 2.8% Nb.
The coefficient of thermal expansion of this alloy is between 10.5 ppm/deg.C and 11 ppm/deg.C.
The above-mentioned palladium-based metal alloy used in the present invention more preferably includes, in atomic percent: 43% Pd, 27% Cu, 10% Ni and 20% P.
The coefficient of thermal expansion of this alloy is between 15 ppm/deg.C and 16 ppm/deg.C.
The balance of the invention is therefore made of a material that makes it possible to use simple manufacturing methods, while having a coefficient of thermal expansion that allows them to be paired with spiral hairsprings made of monocrystalline quartz and/or metal or silicon, preferably made of monocrystalline quartz. The balance according to the invention can also have at least the arm with a coefficient of thermal expansion that allows it to mate with a spiral balance spring of monocrystalline quartz and/or metal or silicon, while having a high inertia by maintaining a compact and aesthetic rim geometry, with a small volume by means of a suitable rim either comprising a portion made of a higher density material or itself made of a higher density material.
Claims (18)
1. Method for manufacturing a balance (1) for a timepiece, said balance (1) comprising a rim (2), a hub (4) and at least one arm (8) connecting said hub (4) to said rim (2), said hub (4) and said arm (8) being made of a metal alloy, said method comprising the steps of:
a) a mould made in the negative shape of the balance (1);
b) obtaining a metal alloy having a coefficient of thermal expansion of less than 25ppm/° c and capable of being in an at least partially amorphous state when heated to a temperature between its glass transition temperature and its crystallization temperature;
c) placing said metal alloy in said mould, heating said metal alloy to a temperature between its glass transition temperature and its crystallization temperature, so as to be thermally moulded and form a balance;
d) cooling said metal alloy to obtain a balance (1) made of said metal alloy;
e) releasing the balance (1) obtained in step d) from its mould;
the method comprises a step of overmoulding a first inertia adjusting member (10) in the rim (2), the first inertia adjusting member (10) being made of a first material having a density greater than the density of the metal alloy.
2. Method for manufacturing a balance for a timepiece, said balance comprising a rim (2), a hub (4) and at least one arm (8) connecting said hub (4) to said rim (2), said hub (4) and said arm (8) being made of a metal alloy, and said rim (2) being made of a second material having a density greater than the density of the metal alloy used for manufacturing said hub (4) and said arm (8), said method comprising the steps of:
a) a mold made in the negative shape of the balance;
a') inserting a rim or rim portions made of a material having a density higher than that of the metal alloy into the mould;
b) obtaining a metal alloy having a coefficient of thermal expansion of less than 25ppm/° c and capable of being in an at least partially amorphous state when heated to a temperature between its glass transition temperature and its crystallization temperature;
c) placing the metal alloy in the mould, heating the metal alloy to a temperature between its glass transition temperature and its crystallisation temperature so as to be hot moulded, and overmoulding the felloe or the felloe portion so as to mould a balance with an insert;
d) cooling the metal alloy to obtain a balance wheel with an insert;
e) releasing the balance obtained in step d) from its mould.
3. A method according to claim 1 or 2, wherein the rim (2) comprises a groove (12) designed to receive a second inertia adjustment and/or unbalance compensation member (14, 15).
4. Method according to claim 1 or 2, characterized in that the rim (2) comprises a groove (12) designed to receive a decorative and/or luminous element.
5. Method according to claim 1 or 2, characterized in that it comprises a step for overmoulding a flexible centring member (16, 17) in the hub (4).
6. Method according to claim 5, characterized in that the integrated flexible centering member (16) is located on the inner circumference of the hub (4).
7. A method according to claim 1 or 2, characterized in that it comprises a step of overmoulding a third flexible inertia adjustment member (19, 20, 22a, 22b) in the arm (8).
8. A method according to claim 1 or 2, wherein the mould has a microstructure forming a decorative piece or a photonic grid.
9. The method according to claim 1 or 2, characterized in that the metal alloy is based on an element selected from the group consisting of platinum, zirconium, titanium, palladium, nickel, aluminum and iron.
10. The method according to claim 1 or 2, wherein the metal alloy is based on platinum and has a coefficient of thermal expansion of less than 12ppm/° c.
11. The method of claim 10, wherein the metal alloy is platinum-based and has a coefficient of thermal expansion between 8ppm/° c and 12ppm/° c.
12. The method of claim 10, wherein the platinum-based metal alloy consists of, in atomic percent:
platinum as the basic component, the amount of which constitutes the balance,
-13% to 17% of copper,
-3% to 7% of nickel,
-20 to 25% phosphorus.
13. The method according to claim 1 or 2, wherein the metal alloy is based on zirconium and has a coefficient of thermal expansion of less than 12ppm/° c.
14. The method according to claim 13, wherein the metal alloy is based on zirconium and has a coefficient of thermal expansion between 8ppm/° c and 11ppm/° c.
15. The method of claim 13, wherein the zirconium-based metal alloy consists of, in atomic percent:
zirconium as the basic component, the content of which constitutes the balance,
-from 14% to 20% of copper,
-12% to 13% of nickel,
-9% to 11% of aluminium,
-2% to 4% niobium.
16. The method of claim 1 or 2, wherein the metal alloy is palladium based and has a coefficient of thermal expansion of less than 20ppm/° c.
17. The method of claim 16, wherein the metal alloy is palladium based and has a coefficient of thermal expansion between 13ppm/° c and 18ppm/° c.
18. The method of claim 16, wherein the palladium-based metal alloy consists of, in atomic percent:
palladium as the basic component, the content of which constitutes the balance,
-25% to 30% of copper,
-from 8% to 12% of nickel,
-18% to 22% phosphorus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110265760.5A CN112965355A (en) | 2017-12-22 | 2018-11-30 | Method for manufacturing balance wheel of clock |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP17210299.8A EP3502787B1 (en) | 2017-12-22 | 2017-12-22 | Method for manufacturing a balance for a timepiece |
| EP17210299.8 | 2017-12-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110265760.5A Division CN112965355A (en) | 2017-12-22 | 2018-11-30 | Method for manufacturing balance wheel of clock |
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| Publication Number | Publication Date |
|---|---|
| CN109960137A CN109960137A (en) | 2019-07-02 |
| CN109960137B true CN109960137B (en) | 2021-04-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202110265760.5A Pending CN112965355A (en) | 2017-12-22 | 2018-11-30 | Method for manufacturing balance wheel of clock |
| CN201811455309.4A Active CN109960137B (en) | 2017-12-22 | 2018-11-30 | Method for manufacturing balance wheel of clock |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202110265760.5A Pending CN112965355A (en) | 2017-12-22 | 2018-11-30 | Method for manufacturing balance wheel of clock |
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| Country | Link |
|---|---|
| US (2) | US11307535B2 (en) |
| EP (2) | EP3502787B1 (en) |
| JP (1) | JP6770049B2 (en) |
| CN (2) | CN112965355A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3796101A1 (en) * | 2019-09-20 | 2021-03-24 | Nivarox-FAR S.A. | Hairspring for clock movement |
| CH716669B1 (en) * | 2019-10-03 | 2023-02-15 | Richemont Int Sa | Method of manufacturing a balance pivot shaft. |
| US20220329102A1 (en) * | 2019-10-10 | 2022-10-13 | NexFi Technology Inc. | Flywheel, flywheel designing method, and flywheel power storage system |
| EP3839646A1 (en) * | 2019-12-18 | 2021-06-23 | The Swatch Group Research and Development Ltd | Oscillating winding mass provided with a decorative element for automatic movement of a timepiece |
| CN115537598B (en) * | 2022-10-10 | 2023-06-20 | 东莞理工学院 | Wide-temperature-range adjustable linear low-thermal-expansion titanium-niobium alloy and preparation method thereof |
| CN115537599B (en) * | 2022-10-13 | 2023-06-06 | 东莞理工学院 | Titanium-niobium alloy with high elastic modulus and near-zero linear expansion coefficient and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004030848A1 (en) * | 2002-09-30 | 2004-04-15 | Liquidmetal Technologies | Investment casting of bulk-solidifying amorphous alloys |
| CN101978327A (en) * | 2008-03-20 | 2011-02-16 | 尼瓦洛克斯-法尔股份有限公司 | Composite pendulum and method for making same |
| EP2395402A1 (en) * | 2010-06-11 | 2011-12-14 | Montres Breguet SA | High frequency balance wheel for timepiece |
| EP3170579A1 (en) * | 2015-11-18 | 2017-05-24 | The Swatch Group Research and Development Ltd. | Method for manufacturing a part from amorphous metal |
| CN107168031A (en) * | 2016-03-07 | 2017-09-15 | 蒙特雷布勒盖股份有限公司 | Adjustable auxiliary temperature compensation system |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US387973A (en) * | 1887-12-02 | 1888-08-14 | Watch-balance | |
| CH621669GA3 (en) * | 1977-12-23 | 1981-02-27 | Method of manufacturing a pivoted clockwork balance and clockwork balance obtained according to this method | |
| EP1258786B1 (en) * | 2001-05-18 | 2008-02-20 | Rolex Sa | Self-compensating spring for a mechanical oscillator of balance-spring type |
| CN101589347A (en) | 2006-12-21 | 2009-11-25 | 康普利计时股份有限公司 | Mechanical oscillator for timepiece |
| EP2104008A1 (en) * | 2008-03-20 | 2009-09-23 | Nivarox-FAR S.A. | Single-body regulating organ and method for manufacturing same |
| EP2703909A1 (en) * | 2012-09-04 | 2014-03-05 | The Swatch Group Research and Development Ltd. | Paired balance wheel - hairspring resonator |
| CH707106B1 (en) | 2012-12-21 | 2014-04-30 | Montres Tudor SA | adjusting screw and watch balance wheel comprising such a screw for adjusting the inertia. |
| CN206178347U (en) | 2015-11-13 | 2017-05-17 | 尼瓦洛克斯-法尔股份有限公司 | Balance, clock cassette mechanism and clock and watch spare with inertia is adjusted |
| EP3182211A1 (en) | 2015-12-17 | 2017-06-21 | Nivarox-FAR S.A. | Composite part with resilient means under stress |
| EP3217228B1 (en) | 2016-03-07 | 2019-08-28 | Montres Breguet S.A. | Bimetal device sensitive to temperature changes |
| EP3252545B1 (en) | 2016-06-03 | 2019-10-16 | The Swatch Group Research and Development Ltd. | Timepiece mechanism with balance wheel inertia adjustment |
-
2017
- 2017-12-22 EP EP17210299.8A patent/EP3502787B1/en active Active
- 2017-12-22 EP EP20201790.1A patent/EP3796102B1/en active Active
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- 2018-10-03 US US16/150,524 patent/US11307535B2/en active Active
- 2018-11-19 JP JP2018216249A patent/JP6770049B2/en active Active
- 2018-11-30 CN CN202110265760.5A patent/CN112965355A/en active Pending
- 2018-11-30 CN CN201811455309.4A patent/CN109960137B/en active Active
-
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- 2022-02-11 US US17/669,476 patent/US11640140B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004030848A1 (en) * | 2002-09-30 | 2004-04-15 | Liquidmetal Technologies | Investment casting of bulk-solidifying amorphous alloys |
| CN101978327A (en) * | 2008-03-20 | 2011-02-16 | 尼瓦洛克斯-法尔股份有限公司 | Composite pendulum and method for making same |
| EP2395402A1 (en) * | 2010-06-11 | 2011-12-14 | Montres Breguet SA | High frequency balance wheel for timepiece |
| EP3170579A1 (en) * | 2015-11-18 | 2017-05-24 | The Swatch Group Research and Development Ltd. | Method for manufacturing a part from amorphous metal |
| CN107168031A (en) * | 2016-03-07 | 2017-09-15 | 蒙特雷布勒盖股份有限公司 | Adjustable auxiliary temperature compensation system |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3796102A1 (en) | 2021-03-24 |
| US20220163923A1 (en) | 2022-05-26 |
| US20190196408A1 (en) | 2019-06-27 |
| JP2019113533A (en) | 2019-07-11 |
| CN112965355A (en) | 2021-06-15 |
| EP3502787B1 (en) | 2020-11-18 |
| EP3796102B1 (en) | 2022-04-20 |
| JP6770049B2 (en) | 2020-10-14 |
| CN109960137A (en) | 2019-07-02 |
| US11307535B2 (en) | 2022-04-19 |
| EP3502787A1 (en) | 2019-06-26 |
| US11640140B2 (en) | 2023-05-02 |
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